Flame retardant polycarbonate composition

ABSTRACT

A flame retardant polycarbonate composition comprising in admixture an aromatic carbonate polymer and a flame retardant additive which may be the metal salts of either monomeric or polymeric phenol ester sulfonic acids, or mixtures thereof.

This invention is directed to a flame retardant polycarbonatecomposition and in particular an aromatic polycarbonate containing inadmixture therewith a particular flame retardant additive which may bethe metal salts of either monomeric or polymeric phenol ester sulfonicacids, or mixtures thereof.

BACKGROUND OF THE INVENTION

With the increasing concern for safety, there is a positive move towardsproviding safe materials for public and household use. One particulararea of need is that of providing flame resistant or flame retardantproducts for use by the ultimate consumer. As a result of this demand,many products are being required to meet certain flame retardantcriteria both by local and federal government and the manufacturers ofsuch products. One particular set of conditions employed as a measuringstandard for flame retardancy is set forth in Underwriters Laboratories,Inc. Bulletin 94. This Bulletin sets forth certain conditions by whichmaterials are rated for self-extinguishing characteristics.

In the art, there are many known flame retardant additives which areemployed by mixing with products to render such materialsself-extinguishing or flame retardant. Such flame retardant additiveshave been known to be employed in amounts of 5 to 20 weight percent inorder to be effective in extinguishing burning of those products whichare combustible. It has also been found that such amounts can have adegrading effect upon the base product to be rendered flame retardant,resulting in the losses of valuable physical properties of the baseproduct. This is particularly so when employing known flame retardantadditives with the base product polycarbonate resins. Many of theseknown additives have a degrading effect upon the polymer.

DESCRIPTION OF THE INVENTION

It has now been surprisingly discovered that an aromatic polycarbonatecan be made flame retardant by incorporating with the aromaticpolycarbonate minor amounts of certain additives, which additives areinert and do not degrade the aromatic polycarbonate. The particularadditive employed herein is unique in that even very minor amountsrender the aromatic polycarbonate flame retardant. The amount of theadditive employed herein can vary, preferably, from 0.01 to about 10weight percent based on the weight of the aromatic polycarbonate.

More specifically, the particular additive of this invention is themetal salt of either the monomeric or polymeric substituted andunsubstituted phenol ester sulfonic acid and includes mixtures thereof.The metal salt employed in the practice of this invention is either thealkali metal or alkali earth metal salt or mixtures of these. The metalsof these groups are sodium, lithium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium and barium.

When the phenol ester sulfonic acid employed in the practice of thisinvention is a substituted phenol ester sulfonic acid, the substituentconsists of an electron withdrawing radical. As employed herein andwithin the scope of this invention, any of the electron withdrawingradicals can be employed in the practice of this invention. However,preferably, the electron withdrawing radical or substituent employed inthe practice of this invention is the halo-, nitro-, trihalomethyl andcyano electron withdrawing radicals or mixtures of these electronwithdrawing radicals.

The electron withdrawing phenomenon, or as it is also referred to aselectronegativity, is defined in Basic Principles Of Organic Chemistryby Roberts and Caserio, 1964 (pp. 185-186), and Physical OrganicChemistry by Jack Hine, McGraw-Hill Book Company, Inc., 1962 (pp. 5, 32and 85-93). Briefly, the electron withdrawing phenomenon is where theradical has a strong affinity for a negative charge, namely electrons,but still remains covalent and does not form an ion. This is anextremely brief description of this phenomenon and is merely set forthhere to describe the electron withdrawing effect. Reference should bemade to the texts set forth above.

In the practice of this invention, the types of sulfonic acids employedherein may be either the monomeric form or the polymeric form ormixtures of these. When first considering the monomeric form, the metalsalt of the unsubstituted and substituted monomeric phenol estersulfonic acid can best be represented by the following formula:

    [R].sub.z {[O.sub.q A].sub.u [X].sub.y [O.sub.r B].sub.v }.sub.m I.

wherein A and B are independently selected from the following formula:

    R'(SO.sub.3 M).sub.n R".sub.p                              II.

wherein R' is an aromatic radical of one to four aromatic nuclei, M is ametal which may be selected from the periodic table of either an alkalimetal or an alkali earth metal, R" is an electron withdrawing radical, nis an integer of 0 to 4 and p is an integer of 0 to 10, provided,however, that the sum of n must be at least 1.

In Formula I above, [R] is an organic radical of 1-20 carbon atoms andis either alkyl, aralkyl, alkenyl, aralkenyl, aryl, arylene, alkylene,aralkylene, alkenylene, aralkenylene, alkylidene, aralkylidene,alkenylidene or aralkenylidene and the group comprising [A] and [B] aswell as a trivalent and tetravalent aromatic nucleus. It should also beunderstood that the radical [R] can also contain halogen substituentswhich would be an electron withdrawing radical and sulfonic acid saltsubstituents. In Formula I, [X] is a di-, tri- or tetravalent radicalselected from the following: ##EQU1## y is an integer of 1-2, m, u, v, qand r are integers of 1-4 and z is an integer of 0- 3, and O is oxygen.

In the above Formula I, the presence of the (SO₃ M) radical on thephenol ester is the novel feature of the instant invention that offersthe excellent flame retardant properties when admixed with an aromaticpolycarbonate.

Actually, while there are many compounds that meet the requirements ofFormula I and which offer excellent flame retardant characteristics toan aromatic polycarbonate, the preferred additive employed in themonomeric form is the sodium salt of the sulfonic acid of dichlorophenyl2,4,5-trichlorobenzenesulfonate. This has the following formula:##SPC1##

When the polymeric form of the unsubstituted and substituted aromaticsulfonic acid is employed in the practice of this invention, it can bestbe represented by the following formula:

    ([R].sub.z {[A][X].sub.y [B].sub.1-3 }).sub.a ([R].sub.z {[A][X].sub.y [B].sub.1-3 }).sub.b                                      III.

wherein [A] and [B] are independently selected from the followingformula:

    (O).sub.q R'(SO.sub.3 M).sub.n R".sub.p                    IV.

wherein (O), R', M, R", n, p and q have the same meaning as citedpreviously. In addition, [R], [X] and z have the same meaning as citedpreviously. Also, the same requirements for n are also applicable. InFormula III, a is an integer of from 0-2000 and b is an integer of from0-2000, provided, however, that the sum of a and b must be at least 4and can be as high as 2000. As shown, the selections of a and b can berandom or equal or one can be zero.

In the practice of this invention, it is to be understood that thepolymeric structure can be either a homopolymer, a copolymer, a randomcopolymer, a block copolymer or a random-block copolymer, or mixtures ofthese polymeric forms. In addition, the ratio of sulfonated phenolicrings to unsubstituted phenolic rings can vary from 1 to 1 to as high asthat which is barely necessary to render the polycarbonate flameretardant and this may be 1 to 1000.

While there are many compounds that meet the requirements of Formula IIIand which offer excellent flame retardant characteristics to an aromaticpolycarbonate, the preferred employment of the instant invention isprovided by the application of Formula III in its simplest form, whichis the metal salt of a sulfonated polycarbonate itself. In this versionthen, the metal sulfonate (SO₃ M) function is attached directly to thepolycarbonate backbone itself, a feature which precludes eventualmigration or plating out phenomena. The sulfonation of thepolycarbonate, which may be a homopolymer of a copolymer (random, blockor random-block copolymer) is then carried out to provide the metalsulfonate (SO₃ M) radical in 0.01 to 10% concentration in the polymer.It is understood that part or all of the effective species may also beintroduced separately by compounding a non-sulfonated polycarbonate witha sulfonated one. In addition, a partially sulfonated polycarbonate mayalso contain fire retardant additives represented by Formulae I and III.It is further understood that mixtures of this version of the instantinvention can also be used.

PREFERRED EMBODIMENT OF THE INVENTION

In order to more fully and clearly illustrate the present invention, thefollowing specific examples are presented. It is intended that theexamples be considered as illustrative rather than limiting theinvention disclosed and claimed herein. In the examples, all parts andpercentages are on a weight basis unless otherwise specified.

EXAMPLE I

Ninety-nine parts of an aromatic polycarbonate, prepared by reacting2,2-bis(4-hydroxyphenyl)propane and phosgene in the presence of an acidacceptor and a molecular weight regulator and having an intrinsicviscosity of 0.57 is mixed with 1 part of a finely ground dehydratedadditive listed in Table I by tumbling the ingredients together in alaboratory tumbler. The resulting mixture is then fed to an extruder,which extruder is operated at about 265°C., and the extrudate iscomminuted into pellets.

The pellets are then injection molded at about 315°C. into test bars ofabout 5 in. by 1/2 in. by about 1/16-1/8 in. thick. The test bars (5 foreach additive listed in the Table) are subject to the test procedure setforth in Underwriters Laboratories, Inc. Bulletin UL-94, Burning Testfor Classifying Materials. In accordance with this test procedure,materials so investigated are rated either SE-O, SE-I or SE-II based onthe results of 5 specimens. The criteria for each SE rating per UL-94 isbriefly as follows:

"SE-O": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 5 seconds and none of the specimens shall dripflaming particles which ignite absorbent cotton.

"SE-I": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the glowing does not travelvertically for more than 1/8 inch of the specimen after flaming ceasesand glowing is incapable of igniting absorbent cotton.

"SE-II": AVerage flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the specimens drip flamingparticles which ignite absorbent cotton.

In addition, a test bar which continues to burn for more than 25 secondsafter removal of the igniting flame is classified, not by UL-94, but bythe standards of the instant invention, as "burns". Further, UL-94requires that all test bars must meet the SE type rating to achieve theparticular rating. Otherwise, the 5 bars receive the rating on the worstsingle bar. For example, if one bar is classified as SE-II and the otherfour (4) are classified as SE-O, then the rating for all 5 bars isSE-II.

The results of the different additives within the scope of the instantinvention are as follows with a control being the aromatic polycarbonateas prepared above without the additive of the type set forth herein.

                                      TABLE 1                                     __________________________________________________________________________                            Flame Out Time                                                                         No. of Drips                                 Additive (1 weight percent)                                                                           Seconds (Avg.)                                                                         Per Test Bar                                                                          Rating                               __________________________________________________________________________       CONTROL              31.6     4+      Burns                                Sodium [phenyl 2,4,5-trichlorobenzene-                                                                6.0      0       SE-I                                 sulfonate]-4'-sulfonate                                                       Calcium [4-bromophenyl 2,4,5-trichloro-                                                               4.0      1.6     SE-II                                benzenesulfonate]-3'-sulfonate                                                Sodium [4,4'-dichlorodiphenyl carbonate]-                                                             3.9      0.8     SE-O                                 2-sulfonate                                                                   Potassium [tris(2-chlorophenyl phosphate]-                                                            5.6      4.0     SE-II                                4-sulfonate                                                                   Barium [bis(4-bromophenyl sulfate]-3-                                                                 7.0      3.0     SE-II                                sulfonate                                                                     Sodium [bis-2,4,5-trichlorophenyl tere-                                                               3.2      0       SE-O                                 phthalate]-x-sulfonate                                                        Disodium [diphenyl oxalate]-4,4'-                                                                     6.6      1.2     SE-II                                disulfonate                                                                   Sodium [phenyl pentachlorobenzenephos-                                                                4.4      0.8     SE-II                                phonate]-4'-sulfonate                                                         Disodium [diphenyl dibromoaleate]-4,4'-                                                               3.3      1.4     SE-II                                disulfonate                                                                   Disodium [BPA-bis(2,4,5-trichlorobenzene-                                                             4.1      0       SE-O                                 sulfonate]-2,2'-disulfonate                                                   Polysodium (bisphenol-A-polycarbonate)                                                                5.0      0.8     SE-I                                 polysulfonate                                                                 Polysodium [(bisphenol-A)-(tetrabromo-                                                                3.9      0       SE-O                                 bisphenol-A)copolycarbonate]-polysulfonate                                    Polysodium [(bisphenol-A)-(tetrachloro-                                                               4.4      0       SE-O                                 bisphenol-A)copolycarbonate]-polysulfonate                                    Sodium [pentachlorophenyl benzoate]-3-                                                                2.8      0       SE-O                                 sulfonate                                                                     Sodium [bis(p-chlorophenyl isophthalate]-                                                             4.2      1.0     SE-II                                5-sulfonate                                                                   Sodium salt of hydroquinone [thionobenzoate]                                  [2',4',5'-trichlorobenzenesulfonate]-2-                                                               3.9      2.0     SE-II                                sulfonic acid                                                                 Potassium (pentachlorophenyl)phenyl methyl-                                                           3.6      0       SE-O                                 phosphonate-4-sulfonate                                                       Sodium 2-chlorophenyl benzenesulfinate-4-                                                             4.6      1.0     SE-II                                sulfonate                                                                     Disodium bis(4-chlorophenyl)succinate 2,2'-                                                           4.6      2.0     SE-II                                disulfonate                                                                   Lithium O-(4'-chlorophenyl) diphenyl-                                                                 2.8      1.0     SE-II                                phosphinothioate-3-sulfonate                                                  Disodium salt of bis(2-chlorophenoxy)                                                                 3.8      2.0     SE-II                                methylphenylsilane 4,4'-disulfonic                                            acid                                                                          __________________________________________________________________________

EXAMPLE II

This Example is set forth to demonstrate the effectiveness ofintroducing the metal sulfonate (SO₃ M) radical directly into thepolycarbonate backbone. The extent of sulfonation is such that the (SO₃M) moiety comprises from 0.01 to up to 10 weight percent of the polymer.

                                      TABLE 2                                     __________________________________________________________________________                         Flame Out Time                                                                         No. of Drips                                    Additive             Seconds (Avg.)                                                                         Per Test Bar                                                                          Rating                                  __________________________________________________________________________       CONTROL           31.6     4+      Burns                                   Polysodium (bisphenol-A-polycarbonate)                                        polysulfonate (containing 1.1 weight                                                               5.8      0.8     SE-I                                    percent (SO.sub.3 Na) radical)                                                Polysodium [(bisphenol-A)-(tetrabromo-                                        bisphenol-A) copolycarbonate]-polysul-                                                             3.0      0.8     SE-O                                    fonate (containing 1.1 weight percent                                         (SO.sub.3 Na) radical and 0.8 weight percent                                  bromine)                                                                      Polysodium [(bisphenol-A)-(tetrachloro-                                       bisphenol-A) copolycarbonate]-polysul-                                                             4.2      0       SE-O                                    fonate (containing 1.1 weight percent                                         (SO.sub.3 Na) radical and 1.3 weight percent                                  chlorine)                                                                     Polysodium (bisphenol-A-polycarbonate)                                        polysulfonate (containing 0.1 weight                                                               8.6      3.2     SE-II                                   percent (SO.sub.3 Na) radical and 1.0 weight                                  percent (bisphenol-A)-polycarbonate-                                          poly(phenylphosphonate) copolymer)                                            Polysodium (bisphenol-A)(isophthalic                                          acid-terephthalic acid)(copolyester                                                                4.2      0       SE-O                                    polycarbonate) polysulfonate (containing                                      2.7 weight percent (SO.sub.3 Na) radical)                                     __________________________________________________________________________

EXAMPLE III

This Example is set forth to demonstrate the effect of the flameretardant additives of this invention at the lower limits of 0.01 weightpercent based on the weight of the polymer composition.

In preparing the test bars for this Example 99.99 parts of thepolycarbonate of Example I is mixed with 0.01 weight percent of theadditives listed in Table 2 employing the same procedure. Test bars arethen molded using the same procedure employed in Example I. The testbars are subjected to the same test procedure of Example I with thefollowing results:

                                      TABLE 3                                     __________________________________________________________________________                           Flame Out Time                                                                         No. of Drips                                  Additive (0.01 weight percent)                                                                       Seconds (Avg.)                                                                         Per Test Bar                                                                          Rating                                                                             Remarks                          __________________________________________________________________________       CONTROL             31.6     4+      Burns                                 Sodium [phenyl 2,4,5-trichlorobenzene-                                                               8.6      2.2     SE-II                                 sulfonate]-4'-sulfonate                                                       Disodium [BPA bis(2,4,5-trichlorobenzene-                                                            11.2     1.6     SE-II                                 sulfonate]-2,2'-disulfonate                                                   __________________________________________________________________________

EXAMPLE IV

This Example is set forth to show the effect of a known commerciallyavailable flame retardant additive.

Example I is repeated except that in place of the additives employedtherein, only 1 part 1,2,5,6,9,10-hexabromocyclododecane is used herein.The results obtained upon evaluating 5 test bars are the same asobtained for the Control shown in Table 1. above.

B

Part A. above is repeated but using 5 weight percent of the aboveadditive, namely 1,2,5,6,9,10-hexabromocyclododecane. The resultsobtained are the same as obtained in Part A. above.

C

Part A. above is repeated but using 10 weight percent of the aboveadditive, namely 1,2,5,6,9,10-hexabromocyclododecane. At this level ofadditive, test bars are rated SE-II. However, the polycarbonate is badlydegraded as evidenced by severe dark streaking of the molded test bars,which degradation does not occur with the additives of the instantinvention.

EXAMPLE V

Example IV is repeated except that hexabromobiphenyl is employed herein.The results obtained are essentially the same as those of Example IV.

EXAMPLE VI

Example IV is repeated except that the additive employed herein is acombination of antimony oxide and a material which is a mixture ofpolychlorinated biphenyl (Aroclor by Monsanto Company). The proportionof the ingredients of the additive employed in this example is based on3 parts of chlorine per 1 part of antimony. The results obtained at 1weight percent and 5 weight percent amounts are the same as in ExampleIV.

However, at the higher amount, namely 10 weight percent, flameretardency effect is noted with, again, severe degradation of thepolycarbonate, as evidenced by the substantial reduction in theintrinsic viscosity of the molded test bars. As molded, the intrinsicviscosity of the test bars is about 0.50. The intrinsic viscosity of themolded test bars containing 10 weight percent of the flame retardantadditive of this Example is 0.253. This shows the severe degradation ofthe polycarbonate when employing this type of well known flameretardant.

In the practice of this invention, aromatic carbonate polymers arerendered flame retardant by the addition of certain particular additiveswhich are the metal salts of substituted and unsubstituted monomeric orpolymeric phenol ester sulfonic acids, or mixtures of these. The amountof the additives employed in the practice of this invention may varyfrom 0.01 to up to that amount which does not cause degradation of thephysical properties of the aromatic carbonate polymer. This is generallyup to 10 weight percent based on the weight of the aromatic carbonatepolymer but may be higher if degradation of the aromatic carbonatepolymer does not occur. Also, in some cases, it has been found thatabove 10 weight percent level, no added advantage in flame retardancyhas been observed. The amount of the additive to be employed can also bea function of the degree of flame retardancy desired.

The novelty of the instant invention is achieved by the introduction ofthe sulfonic radical (SO₃ M) into the aromatic rings of the phenolicesters. It is not exactly understood how the additive of this inventionfunctions or how such minor amounts can act as an effective flameretardant for the aromatic carbonate polymer. Analysis of thecomposition of this invention after being subjected to a firetemperature of about 600°C. showed an unusually high percentage ofremaining char. This leads one to hypothesize that the additive may actas a cross-linking agent when the aromatic carbonate polymer issubjected to fire temperatures.

As indicated previously, the additive of the instant invention comprisesthe alkali or alkali earth metal salts of the substituted andunsubstituted monomeric or polymeric phenolic ester sulfonic acids ormixtures of these. While a great number of such salts are set forth inthe tables of the Examples of the instant invention, these are only arepresentative sample of the additives of this invention. The sodium,calcium, magnesium, potassium, strontium, lithium, barium, rubidium andcesium salts of other aromatic sulfonic acids can be employed in placeof those of the Examples with the same effective flame retardancy beingachieved. These other aromatic sulfonic acids are:

triphenyl trimellitate disulfonic acid

4-chlorophenyl thionobenzoate sulfonic acid

4,4'-dichlorodiphenylsulfite disulfonic acid

4,5-dibromophenyl benzenesulfonate sulfonic acid

diphenyl sulfate sulfonic acid

tri(α-naphthyl)phosphate trisulfonic acid

hydroquine bis(phenyl phenylphosphonate)sulfonic acid

tetrabomobisphenol-A-bis(4-chlorophenyl sulfate) disulfonic acid

diphenyl dibromomaleate disulfonic acid

bisphenol-A-bis[bis(4-chlorophenyl)thiophosphate] disulfonic acid

poly(diphenylsiloxane)polysulfonic acid

poly(bisphenol-A-tetrachlorobisphenol-A)polysulfonic acid

bisphenol-A-bis(2,4,5-trichlorobenzenesulfonate)sulfonic acid

In the practice of this invention, the additive or the sulfonatedpolymer are prepared by sulfonation methods well known in the art. Forexample, one sulfonates the phenol ester or the (phenol ester) polymer(such as the polycarbonate) by subjecting it, in solution, to the actionof liquid SO₃ and by neutralizing the resultant sulfonic acid. The saltis then recovered by precipitation or by distillation of the solvent.

In the practice of this invention, any of the aromatic polycarbonatescan be employed herein. However, particularly useful are the aromaticpolycarbonates prepared by reacting a dihydric phenol, such asbisphenol-A (2,2'bis(4 hydroxyphenyl)propane) with a carbonateprecursor. Typical of some of the dihydric phenols that may be employedin the practice of this invention are bis(4-hydroxyphenyl)methane,2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxy-3-methylphenyl)propane,4,4-bis(4-hydroxyphenyl)heptane,2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane,2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane,(3,3'-dichloro-4,4'-dihydroxydiphenyl)methane. Other dihydric phenols ofthe bisphenol type are also available and are disclosed in U.S. Pat.Nos. 2,999,835, 3,028,365 and 3,334,154.

In addition, the reaction is carried out with the carbonate precursor inthe presence of a molecular weight regulator, an acid acceptor and acatalyst. The preferred carbonate precursor generally employed inpreparing carbonate polymers is carbonyl chloride. However, othercarbonate precursors may be employed and this includes other carbonylhalides, carbonate esters or haloformates.

The acid acceptors, molecular weight regulators and catalysts employedin the process of preparing polycarbonates are well known in the art andmay be any of those commonly used to prepare polycarbonates.

As stated previously, mixtures can be employed herein. These mixturescan consist of, for example, (a) mixtures of metal salts ofunsubstituted and substituted monomeric phenol ester sulfonic acids, (b)mixtures of metal salts of unsubstituted and substituted polymericphenol ester sulfonic acids, (c) mixtures of (a) and (b), and (d)mixtures of any of the above with metal salts of sulfonic acidsubstituted carbonate polymers. The mixtures herein offer certainadvantages in providing flame retardancy of SE-O rating of 5 test barsand essentially no drips per bar.

It will thus be seen that the objects set forth above among those madeapparent from the preceding description are efficiently attained andsince certain changes may be made in carrying out the above process andin the composition set forth without departing from the scope of thisinvention, it is intended that all matters contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:
 1. A flame retardant carbonate polymer compositioncomprising in admixture a carbonate polymer and a minor amount of ametal salt of an unsubstituted and substituted monomeric phenol estersulfonic acid and mixtures thereof, wherein the metal salts are selectedfrom the group consisting of the alkali metal salts and alkali earthmetal salts and mixtures of these metal salts, and the substituent onthe metal salts of the substituted monomeric phenol ester sulfonic acidis selected from the group consisting of an electron withdrawingradical, and mixtures of electron withdrawing radicals.
 2. Thecomposition of claim 1 wherein the admixture comprises 0.01 to about 10weight percent of the additive based on the weight of the aromaticcarbonate polymer composition.
 3. The composition of claim 1 wherein theelectron withdrawing radical is selected from the group consisting ofhalo-, nitro-, trihalomethyl- and cyano- radicals, and mixtures thereof.4. The composition of claim 1 wherein the metal salt of theunsubstituted and substituted monomeric phenol ester sulfonic acid hasthe following formula:

    [R].sub.z {[O.sub.q A].sub.u [X].sub.y [O.sub.r B] .sub.v }.sub.m I.

wherein A and B are independently selected from the following formula:

    R'(SO.sub.3 M).sub.n R".sub.p                              II.

wherein R' is an aromatic radical of 1- 4 aromatic nuclei, M is a metalselected from the group consisting of alkali metal and alkali earthmetal, R" is an electron withdrawing radical, n, q and r are integers offrom 1-4, n and v are integers of from 0-4 and p is an integer of from0- 10; provided that the sum of n when employed in Formula I must be atleast 1; and further, wherein in Formula I, [R] is an organic radical of1-20 carbon atoms and is selected from the group consisting of alkyl,aralkyl, alkenyl, aralkenyl, aryl, arylene, alkylene, aralkylene,alkenylene, aralkenylene, alkylidene, aralkylidene, alkenylidene,aralkenylidene, A and B, z is an integer of from 0-3, [X] is selectedfrom the group consisting of ##EQU2## y is an integer of from 1-2, m isan integer of from 1-4 and O is oxygen.
 5. The composition of claim 4wherein the electron withdrawing radical is chlorine.
 6. The compositionof claim 4 wherein the metal salt is [R]_(z) ([(O)_(q) R'(SO₃ M)_(n)R"_(p) ][X]₂ and the sum of n equals
 2. 7. The composition of claim 4wherein the metal salt is sodium [4,4'-dichlorodiphenylcarbonate]-2-sulfonate.
 8. The composition of claim 4 wherein the metalsalt is disodium [diphenyl oxalate]-4-sulfonate.
 9. The composition ofclaim 4 wherein the metal salt is sodium [phenyl2,4,5-trichlorobenzenesulfonate]-4'-sulfonate.